Anthraquinone dyestuff



'materials in the various shades of blue. A difllculty encountered in using anthraquinone dyestufls which color organic derivative of cellulose Patented Feb. s, 1945 UNITED STATES PATENT orri-cs mnneoumonn DYESTUFF George W. Seymour and Barnard Theodore Pull, Cumberland, Md., assignors to Celanese Cor- A notation of America, a corporation of Delaware No Drawing.

8 Claims.

This invention relates to the manufacture .of dyestufis oi the anthraquinone series and relates more particularly to the manufacture of dyestuil's which are valuable i'or'the coloration of textile materials comprising organic derivatives of cellulose.

An object of our invention is the-preparation of anthraquinone dyestufls for the coloration of organic derivative of cellulose materials. Another object of our invention is the preparation of anthraquincne dyestuils' which may be used for the coloration 01' organic derivative of cellulose materials to produce fast colors which are highly resistant to acidfading.

' Other objects of our invention will appear from the following detailed description.

Many dyestuiis' of the anthraquinone series which have been prepared are useful forthe coloration of organic derivative of cellulose materials such as organic esters and organic ethers of cellulose. These anthraquinone dyestuffs have been obtained in numerous colors and among these some of the most valuable are those derivatives which color organic derivative of cellulose materials in various shades of blue is that while the colors are resistant to changes caused by the usual agencies which textile materials must withstand, they are. not sumciently resistant to fad- 7 ing when the colored materials are exposed to the duced by the products of combustion of coal, gas,

etc., and changes in shade frequently result. In some casesthe change produced is a dulling oi the brightness 'oi'the' color and inothers the material takes on a noticeably redder hue. Such changes naturally restrict the range of usefulness of these dyestuffs and produce considerable consumer sales resistance to the purchase or other articles of such shade. y

We have now discovered that anthraqulnone dyestufiswhich dyeorganic derivative of cellulose materials in desirable green-blue shades and which are highly resistant.to acid fading may be' obtained by the condensation of hydroxylaminoanthraquinones with lower aliphatic aldehydes in lytlc agents.

I Various lower aliphatic jaldehydes may be used ior condensation with" hydroxymmlno-anthra,

'quinones to form the acid' iae't dyestuffs of our invention; Among-the suitable aldehydes may mentioned formaldehyde. acetaldehyde, outyralaction of an acid atn'iosphere such as that pro- Application November 28, 1940, 3 Serial No. 367,630

yield particularly valuable dyestufis. The condensation reaction may be carried out by refluxing the particular hydroxylamino-anthraqulnone and the aldehyde with which it is to be condensed vent. Solvents such as ethyl alcohol, methyl alcohol, dioxane, butyl alcohol, and ethylene formal may be used. Preferably the reaction is carried out using ethyl alcohol as the solvent. The temperature at which the refluxing takes place will of, course vary depending upon the particular solvent which is being used. When ethyl alcohol is used, the reflux temperature will be at out 781C. ,The condensation reaction may be carried out at temperatures from about 50 0. up to 150 C. using a'suitable inert solvent.

Whilethe condensation reaction may be car ried out without the aid of catalytic agents, it is preferable that the reaction be carried out in, the presence of a catalyst. Suitable catalytic agents are such metal salts as copper sulfate, tin sulfate, cupric chloride, stannous chloride, andthe like,

but preferably we use cupricchlorlde. -'1he cats-- lyst may be used in an' amount varying from about 1 to 10% based on the weight of the an- I thraquinone derivative being condensed.

The time necessary for completion of the condensation reaction will also vary depending upon.

the particular reactants being employed. Gen erally, refluxing from 2 to 10 hours is sufllcient to obtain dyestuils exhibiting suitable resistance to acid fading. Further refluxing beyond the optimum time necessary for preparing a particular dyestuil maybe 'carrled out, if desired, to vary the shade of'the dyestu'fl.

an inert solvent in the presence of certain'catai The dyestuffs may be used in various ways. They may be applied by a vat process in the leuco or reduced. form and then oxidized to the desired color or they may be applied in solution when sufllciently soluble, in aqueous suspension 5 or in colloidal form. When used on 'organlcderivative of cellulose materials, these dyestufls may be applied in any manner as by dyeing, printing, stencilling or other method of local application.

53 The coloring matters oi-o'urinventlon' are parin the presence of a suitable inert organic sol-.

dried and milledto ticularly applicable for the coloration of organic derivatives of cellulose such as cellulose esters and cellulose ethers. Examples of such esters are cellulose acetate, cellulose propionate, cellulosebutyrate, and mixed esters such as cellulose acetopropionate and cellulose aceto-butyrate. Exam- .ples of cellulose others are ethyl cellulose and ferent shades by means of other dyestuffs, before,

after or simultaneously with the coloration of the cellulose esters or ethers.

' In order further to illustrate our invention but without being limited thereto the following examples are given:

Example I 30 parts by weight of 4,8-di-hydroxylamino-.

anthrarufine prepared by reducing 4,8-dinitro anthraruflne with stannous chloride and caustic soda are reacted with 20 parts of 40% formaldehyde in 250 parts of ethyl alcohol. The mixture-'- is refluxed for 8 hours, cooled to 70 C. and the resulting dyestufl is separated'by filtration.

25 parts of the dyestuif isolated in this manner are milled in a ball mill with an equal weight of Turkey red oil until the dyestufi is entirely dispersed. The color may then'be standardized as desired by the addition of dextrin, sodium sulfate or other diluent, the. material then being heated with steam and diluted with water and powder form. The powdered dyestuif is then dispersed in a solution of so-- dium sulfo-naphthalene ricinoleate, the mixture 40 then added to the dye-bath which is held to pH 5-7.5. A cellulose acetate fabric is entered in the dye-bath and full color value with good exhaustion of the dye-bath is obtained in one hour at 75 to 85 C. a

The material dyed in a green-blue shade in the above manner with this dyestuif shows excellent fastness properties when subjected to theaction of an atmosphere containing combustion gases for 20 hours and good fastness at 40 hours.

40 hours is sumcient commercial resistance for any dyestufl. a

, Example II The reactants are refluxed for 7 hours, cooled to room temperature,

and the resulting dyestufi isolated by filtration. A dye-bath is prepared with this dyestufl in the manner indicated in Example I and a cellu lose acetate material isdyed therein. The resulting fabric dyed in a green-blue shade shows a very high degree of fastness to acid fading.

Example III blue shades resistant to acid fading.

It is to be understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing fromthe spirit of our invention.

Having described our invention, what we desire to secure by Letters Patent is:

1. Process for the dyestuffs fast to condensingan aliphatic aldehyde with a 4,8-1dihydroxylamino-anthraruflne. 1

2. Process for the production of an anthraquinone dyestufl fast to acid fading, which comprises condensing formaldehyde with 4,8-di-hydroxylamino-anthrarufine.

3. Anthraquinone dyestuffs fast to acid fading produced by condensing an aliphatic aldehyde with 1,8-di-hydroxylamino-anthrarufine.

4. An anthraquinone dyestuff which dyes in green-blue shades fast to acid fading produced by condensing formaldehyde with 4,8-di-hydrox: ylam-ino-anthrarufine.

5. Th processof coloring material made of or plying thereto an anthraquinone dyestufl which 5 is produced bycondensing an aliphatic aldehyde with 4,8'-di-hydroxylamin -anthrarufine. I

'7. Material made of or containing an organic derivative of cellulose colored with an anthraquinone dyestufi fast to acid fading produced by condensing an aliphatic aldehyde with 4,8-dihydroxylamino-anthrarufine. V 8. Material made of or containing cellulose acetate colored with an anthraquinone, dyestufi which is produced by, condensing an aliphatic aldehyde with 4,8-di-hydroxylamino-anthrarufine.

' GEORGE W. SEYMOUR.

BURNARD THEODORE PULL;

the resulting dyestufi production of anthraquinon v acid fading, which comprises 

